O objetivo deste trabalho foi o de avaliar o desempenho de um reator de leito estruturado submetido à aeração intermitente (LEAI) na remoção de matéria orgânica e nitrogênio de esgoto sanitário. O reator apresentava um volume total de 11,6 L, com uma porosidade do leito de 52%. O leito estruturado era composto de 13 estruturas cilíndricas (diâmetro igual a 3 cm) de espuma de poliuretano, dispostas verticalmente no interior do reator. A alimentação do reator era feita continuamente com esgoto sanitário, sendo este proveniente de um interceptor de esgoto que passava próximo ao laboratório onde o sistema foi montado. O reator era provido de sistema de recirculação interna, com razão de recirculação igual a 3, valor este adotado após a realização de ensaios hidrodinâmicos. Foram testadas 4 condições operacionais diferentes, variando-se o tempo de detenção hidráulica (TDH) e os períodos de aeração e não aeração. Para cada condição operacional, foram feitos os seguintes estudos: avaliação da eficiência de remoção de matéria orgânica e nitrogênio, determinação da atividade nitrificante e desnitrificante, determinação do número mais provável (NMP) da comunidade nitrificante e desnitrificante, perfis temporais e análise da comunidade microbiana. O sistema apresentou elevada remoção de N-total, com valores médios de 80% para valores de TDH de 12 e 10 horas, sob 2 horas de aeração e 1 hora sem aeração. Com a diminuição do TDH para 8 horas, houve queda na eficiência do sistema para 70% (mantendo-se os períodos de aeração de 2 horas e não aeração de 1 hora). Alterando-se o período de aeração para 3 horas, mantendo-se em 1 hora o período sem aeração, o reator apresentou eficiência média de remoção de N-total de 79% com o TDH de 8 horas. A remoção de DQO foi elevada em todas as fases, com valores médios em torno de 90%. Os resultados da atividade nitrificante e desnitrificante foram condizentes com valores encontrados na literatura para sistemas que operam com remoção simultânea de matéria orgânica e nitrogênio. Os perfis temporais mostraram que não houve variação nas formas de nitrogênio (N-NH4+, N-NO2- e N-NO3-) no efluente, apesar da operação sob a aeração intermitente devido ao grau de mistura imposto pela recirculação interna. A concentração de sólidos no efluente foi relativamente baixa quando comparada à concentração de efluentes de reatores de biomassa suspensa, com valor máximo de SSV igual a 108mgSSV.L-1. A presença do Metazoário Aelosomas sp no efluente do reator indica um possível consumo do lodo excedente no reator por esses microrganismos. As análises microbiológicas mostraram uma elevada abundância relativa de gêneros aeróbios facultativos, capazes de utilizar N-NO3- e N-NO2- como receptor de elétrons na ausência de oxigênio. Também se verificou a presença do gênero Comamonas sp em elevada abundância relativa. Esse gênero apresenta microrganismos capazes de realizar a nitrificação heterotrófica e a desnitrificação aeróbia. No entanto, os ensaios realizados não permitem inferir sobre a ocorrência desses processos. Desse modo, os processos convencionais de nitrificação e desnitrificação, tanto pela estratificação do biofilme devido à formação de gradiente de concentração de oxigênio dissolvido, quanto devido à aeração intermitente, certamente tiveram papel preponderante na remoção de nitrogênio. Os resultados obtidos permitem considerar o reator LEAI como uma alternativa tecnicamente viável para a remoção simultânea de matéria orgânica e nitrogênio de esgotos sanitários. / This study aimed at evaluating the organic matter and nitrogen removal from sewage in a structured bed reactor subjected to intermittent aeration. The reactor had a total volume of 11.6 L and bed porosity of 52%. Thirteen polyurethane foam cylinders of 3 cm diameter and 60 cm height were fixed vertically inside the reactor using PVC rods. The reactor was continuously fed with sewage collected from a sanitary sewer passing near the laboratory where the system was assembled. The reactor was provided with internal recirculation system with a recirculation ratio at 3, a value adopted after conducting hydrodynamic tests. Four different operating conditions were tested, varying the hydraulic retention time (HRT) and aeration and non-aeration periods. Nitrogen and organic matter removal efficiencies, nitrifying and denitrifying activities, and the most probable number (MPN) of nitrifying and denitrifying communities were evaluated for each operational condition. The reactor presented a Total-N removal efficiency of 80%, at HRT of 12 hours and 10 hours and aerated and non-aerated periods of 2 hours and 1 hour, respectively. With decreasing the HRT to 8 hours, the Total-N removal efficiency decreased to 70% for the same aeration and non-aeration periods. After increasing the aerated period to 3 hours and keeping the non-aerated periods of 1 hour and HRT of 8 hours, the system attained the Total-N removal efficiency of 79%. COD removal efficiencies were about 90% in all operational condition. Nitrifying and denitrifying activities were similar to those found in the literature for systems presenting simultaneous nitrification and denitrification, and carbon removal. No variation in nitrogen forms (NO3--N, NO2--N and NH4+-N) was observed during a cycle of intermittent aeration. The solids concentration in effluent was relatively low compared to the concentration of suspended-growth biomass reactors, with a maximum value of VSS of 108 mgVSS.L-1. The presence of the metazoan Aelosomas sp in the effluent in all operational conditions indicated a possible use of the excess sludge in the reactor by these microorganisms. Microbiological analysis showed a high relative abundance of aerobic/facultative microorganisms, capable to use NO3--N and NO2--N as electron acceptor in the absence of oxygen. It was also verified the presence of the genus Comamonas sp with high relative abundance. This genus presents microorganisms able to perform heterotrophic nitrification and aerobic denitrification. However, the assays do not allow us to infer the occurrence of these processes. Thus, the conventional processes of nitrification and denitrification certainly played a preponderant role in nitrogen removal both by the stratification of the biofilm due to the formation of a concentration gradient of dissolved oxygen, as due to the intermittent aeration. The results allow considering the reactor as a viable technological alternative for the simultaneous removal of organic matter and nitrogen of sewage.

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active biomolecules such as DNA bases and neurotransmitters. The results highlight a simplified surface modification procedure for producing efficient and highly selective electrocatalysts. The next four chapters focus on evaluating nitrogen-doped carbon nano-onions (𝑛-CNOs) as electrocatalysts for oxygen reduction and CO2 reduction. 𝑛-CNOs exhibit excellent electrocatalytic performance toward O2 to H2O reduction, which is a pivotal process in fuel cells. 𝑛-CNOs demonstrate excellent resistance against CO poisoning and long-term stability compared to state-of-the-art Pt/C catalysts. In CO2 electrochemical conversion, 𝑛-CNOs demonstrate significant improvement in catalytic performance toward reduction of CO2 to CO with a low overpotential and high selectivity. The outstanding catalytic performance of 𝑛-CNOs originates from the asymmetric charge distribution and creation of catalytic sites during incorporation of nitrogen atoms. High contents of pyridinic and graphitic N are critical for high catalytic performance. This work suggests that carbon-based materials can be outstanding alternatives to traditional metal-based electrocatalysts when their microstructures and surface chemistries are properly tailored.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Carbon nanotubes (CNTs) are well known as excellent electrical conductors. However, their transport properties are limited by electrical breakdown in ambient. Moreover, the electronic properties can further be modulated by doping. Devices such as Schottky diodes, transistors and logic gates based on un-doped and doped CNT junctions have been realized. Recently, nitrogen doped CNTs show potential application in replacing platinum cathode catalyst in fuel cell technology. We synthesize pristine, nitrogen-doped and nitrogen-doped:pristine CNT intratubular junctions by one-step co-pyrolysis and explore them for different applications. We show that the position of electrical breakdown can be predicted which is essential to know for high current applications. Among other applications, we show that individual CNT intratubular junction exhibits rectifying characteristics. Further investigation indicates the intratubular junction behaves like Schottky diode. Lastly, the potential replacement of platinum by nitrogen doped CNTs in direct methanol fuel cell has been explored.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 5 uppsatser.

Diss. (sammanfattning) Umeå : Umeå universitet, 2008. / Härtill 3 uppsatser.

Thesis (M.S.)--Oregon State University, 2006. / Printout. Includes bibliographical references (leaves 27-31). Also available on the World Wide Web.

Neste trabalho foi desenvolvido um procedimento experimental para a fabricação de estruturas 3D de nanotubos de carbono crescidos sobre substrato de cobre e decorados com partículas de óxido de titânio. Foram relacionados os três tipos diferentes de NTCs nesta estrutura (simples, dopados com nitrogênio e tratados com plasma) com a deposição do TiO2 por ALD. Foram igualmente propostas três aplicações para esta estrutura. A síntese dos NTCs verticalmente orientados, dopados e não dopados, foi otimizada dentre alguns parâmetros de síntese como temperatura, agente oxidante e principalmente, o filme catalisador. A introdução de defeitos nos NTCP através do tratamento a plasma oxidativo foi avaliada frente a variáveis como pressão, potência e tempo de exposição. A relação entre os defeitos destes três tipos de NTCs e a deposição de TiO2 por ALD foi avaliada por microscopia eletrônica de transmissão, Raman, XPS e TGA. O procedimento experimental para confecção da estrutura 3D foi desenvolvido etapa por etapa via diversas técnicas experimentais, desde caracterização química, imagem, até testes empíricos. Na estrutura final, foram avaliadas as propriedades fotocatalíticas pela decomposição de corante orgânico em meio aquoso, propriedades capacitivas por voltametria cíclica e propriedades de emissão por campo através de curvas de campo elétrico por corrente de emissão e diagramas F-N. Foram obtidas florestas de NTCs de boa qualidade com até 0.5mm de altura, de diâmetros e número de paredes regulares. Nestes foi possível introduzir defeitos de maneira controlável, mantendo o arranjo da floresta. As florestas de NTCNx alcançam uma altura de até 0,3mm com concentração de nitrogênio de 2% tendo os nanotubos uma estrutura típica “bamboo-like”. Os resultados mostram a relação entre o tipo de defeito e a deposição de TiO2 por ALD, obtendo-se partículas cristalinas para os NTCP e NTCNx, sendo neste ultimo as partículas homogeneamente distribuídas e com tamanho uniforme, enquanto nos NTCOx forma-se uma densa camada de TiO2 composta por grandes grãos monocristalinos A partir de processo como tratamentos térmicos e transferência dos NTC de substrato foi possível obter uma estrutura 3D composta de uma camada carbono grafítico e NTC-VAs sobre um substrato de cobre, sem alterar o arranjo inicial das florestas. As amostras mostraram efeito de emissão de elétrons por campo elétrico, porém estas requerem uma análise mais quantitativa. Os ensaios de fotocatálise mostraram que a imobilização do TiO2 em um suporte denso inviabiliza a degradação do corante em meio aquoso. Os NTCNx apresentaram maior capacitância que as mostras de NTCP, e o TiO2 foi aparentemente ineficaz para a melhoria desta propriedade. / In this work, we propose an experimental procedure for fabrication of 3D carbon nanotubes structures anchored with titanium oxide particles, on a copper substrate. We correlate three different types of CNTs from this structure (pristine, doped with nitrogen and treated with plasma) with the deposition of TiO2 by ALD. It was yet suggested, three applications for this structure. The synthesis of vertically aligned CNTs, doped and undoped, was optimized among several synthesis parameters such as temperature, oxidizing agent and specially, the catalyst film. The introduction of defects in NTCP by oxidative plasma treatment was evaluated against variables such as pressure, power and exposure time. The association between the defects from these three types of CNTs and the deposition of TiO2 by ALD was assessed by transmission microscopy, Raman, XPS and TGA. The experimental procedure for assembling the 3D structure had been studied step by step by various techniques, from chemical and imaging, up to empirical testing. In the final structure, the photocatalytic properties were evaluated by the organic dye decomposition in an aqueous medium, capacitive properties by cyclic voltammetry and field emission properties through electric field versus emission current curves and F-N diagram. Was obtained high quality NTCs with a height up to 0.5mm with regular diameters and number of walls. On these, it was introduced, in a controllable way, a high amount of defects without jeopardizing the forest structure. The NTCNx forest reach a 0,3nm height with a 2% nitrogen concentration in its typical structure “bamboo-like”. The results show the relation between the type of defect and the deposition of TiO2 by ALD, forming crystalline particles over the NTCP and NTCNx, in this last evenly distributed with uniform size, while on the NTCOx is is formed a dense TiO2 layer shaped by large monocrystalline grains. By process such as heat treatments and CNT transferring was achieved a 3d structure composed by a graphitic carbon layer and VACNTs over a cupper substrate, without disturb the forest assembly. The samples showed electron field emission effect, but its assessment for quantitative analysis was limited to technical issues. The photocatalysis tests showed that immobilization of TiO2 on a dense support prevents the dye degradation in an aqueous medium. The NTCNx shown higher capacitance than NTCP, and the TiO2 was apparently ineffective for improvement of this property.

Neste trabalho foi desenvolvido um procedimento experimental para a fabricação de estruturas 3D de nanotubos de carbono crescidos sobre substrato de cobre e decorados com partículas de óxido de titânio. Foram relacionados os três tipos diferentes de NTCs nesta estrutura (simples, dopados com nitrogênio e tratados com plasma) com a deposição do TiO2 por ALD. Foram igualmente propostas três aplicações para esta estrutura. A síntese dos NTCs verticalmente orientados, dopados e não dopados, foi otimizada dentre alguns parâmetros de síntese como temperatura, agente oxidante e principalmente, o filme catalisador. A introdução de defeitos nos NTCP através do tratamento a plasma oxidativo foi avaliada frente a variáveis como pressão, potência e tempo de exposição. A relação entre os defeitos destes três tipos de NTCs e a deposição de TiO2 por ALD foi avaliada por microscopia eletrônica de transmissão, Raman, XPS e TGA. O procedimento experimental para confecção da estrutura 3D foi desenvolvido etapa por etapa via diversas técnicas experimentais, desde caracterização química, imagem, até testes empíricos. Na estrutura final, foram avaliadas as propriedades fotocatalíticas pela decomposição de corante orgânico em meio aquoso, propriedades capacitivas por voltametria cíclica e propriedades de emissão por campo através de curvas de campo elétrico por corrente de emissão e diagramas F-N. Foram obtidas florestas de NTCs de boa qualidade com até 0.5mm de altura, de diâmetros e número de paredes regulares. Nestes foi possível introduzir defeitos de maneira controlável, mantendo o arranjo da floresta. As florestas de NTCNx alcançam uma altura de até 0,3mm com concentração de nitrogênio de 2% tendo os nanotubos uma estrutura típica “bamboo-like”. Os resultados mostram a relação entre o tipo de defeito e a deposição de TiO2 por ALD, obtendo-se partículas cristalinas para os NTCP e NTCNx, sendo neste ultimo as partículas homogeneamente distribuídas e com tamanho uniforme, enquanto nos NTCOx forma-se uma densa camada de TiO2 composta por grandes grãos monocristalinos A partir de processo como tratamentos térmicos e transferência dos NTC de substrato foi possível obter uma estrutura 3D composta de uma camada carbono grafítico e NTC-VAs sobre um substrato de cobre, sem alterar o arranjo inicial das florestas. As amostras mostraram efeito de emissão de elétrons por campo elétrico, porém estas requerem uma análise mais quantitativa. Os ensaios de fotocatálise mostraram que a imobilização do TiO2 em um suporte denso inviabiliza a degradação do corante em meio aquoso. Os NTCNx apresentaram maior capacitância que as mostras de NTCP, e o TiO2 foi aparentemente ineficaz para a melhoria desta propriedade. / In this work, we propose an experimental procedure for fabrication of 3D carbon nanotubes structures anchored with titanium oxide particles, on a copper substrate. We correlate three different types of CNTs from this structure (pristine, doped with nitrogen and treated with plasma) with the deposition of TiO2 by ALD. It was yet suggested, three applications for this structure. The synthesis of vertically aligned CNTs, doped and undoped, was optimized among several synthesis parameters such as temperature, oxidizing agent and specially, the catalyst film. The introduction of defects in NTCP by oxidative plasma treatment was evaluated against variables such as pressure, power and exposure time. The association between the defects from these three types of CNTs and the deposition of TiO2 by ALD was assessed by transmission microscopy, Raman, XPS and TGA. The experimental procedure for assembling the 3D structure had been studied step by step by various techniques, from chemical and imaging, up to empirical testing. In the final structure, the photocatalytic properties were evaluated by the organic dye decomposition in an aqueous medium, capacitive properties by cyclic voltammetry and field emission properties through electric field versus emission current curves and F-N diagram. Was obtained high quality NTCs with a height up to 0.5mm with regular diameters and number of walls. On these, it was introduced, in a controllable way, a high amount of defects without jeopardizing the forest structure. The NTCNx forest reach a 0,3nm height with a 2% nitrogen concentration in its typical structure “bamboo-like”. The results show the relation between the type of defect and the deposition of TiO2 by ALD, forming crystalline particles over the NTCP and NTCNx, in this last evenly distributed with uniform size, while on the NTCOx is is formed a dense TiO2 layer shaped by large monocrystalline grains. By process such as heat treatments and CNT transferring was achieved a 3d structure composed by a graphitic carbon layer and VACNTs over a cupper substrate, without disturb the forest assembly. The samples showed electron field emission effect, but its assessment for quantitative analysis was limited to technical issues. The photocatalysis tests showed that immobilization of TiO2 on a dense support prevents the dye degradation in an aqueous medium. The NTCNx shown higher capacitance than NTCP, and the TiO2 was apparently ineffective for improvement of this property.